CN1938085A - Palladium, tungsten and zirconium-based catalyst for production of oxygen-containing compound, production process of the catalyst, and production process of oxygen-containing compound using the cataly - Google Patents

Palladium, tungsten and zirconium-based catalyst for production of oxygen-containing compound, production process of the catalyst, and production process of oxygen-containing compound using the cataly Download PDF

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CN1938085A
CN1938085A CNA2005800106062A CN200580010606A CN1938085A CN 1938085 A CN1938085 A CN 1938085A CN A2005800106062 A CNA2005800106062 A CN A2005800106062A CN 200580010606 A CN200580010606 A CN 200580010606A CN 1938085 A CN1938085 A CN 1938085A
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catalyst
oxygenatedchemicals
prepare
oxygen
palladium
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奥原敏夫
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Resonac Holdings Corp
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Showa Denko KK
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    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J23/56—Platinum group metals
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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    • B01J23/56—Platinum group metals
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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Abstract

A catalyst for the production of an oxygen-containing compound, comprising palladium, tungsten and zirconium, a production process thereof, and a production process of an oxygen-containing compound using the catalyst. The catalyst can provide an oxygen-containing compound from a lower olefin and oxygen with high productivity and high selectivity.

Description

Be used to prepare palladium, tungsten and the Zirconium-base catalyst of oxygenatedchemicals, this Preparation of catalysts method and the method for utilizing this Preparation of Catalyst oxygenatedchemicals
The application requires U.S. Provisional Application No.60/558, the priority in 557 (date of filing on April 2nd, 2004).
Technical field
The present invention relates to be used to prepare the catalyst of oxygenatedchemicals, this Preparation of catalysts method and the method for utilizing this Preparation of Catalyst oxygenatedchemicals, this catalyst is used for generating oxygenatedchemicals by alkene and oxygen in gas phase.
More specifically, the present invention relates to be used to the new catalyst for preparing oxygenatedchemicals (for example acetate), comprise tungsten, zirconium and palladium, this Preparation of catalysts method and utilize the method for this Preparation of Catalyst oxygenatedchemicals.
Background technology
So far, existing many researchs are devoted to be obtained by alkene and oxygen the method for oxygenatedchemicals.
Especially, about generate the catalyst of acetate by one step of ethene and oxygen, the liquid phase one-step oxidation method has for example been proposed, wherein use the right oxidation reduction catalyst of the metal ion that comprises for example palladium-cobalt and palladium-iron (referring to patent document 1 (French Patent (FRP) No.1,448,361)); Wherein use the method (patent document 2 (Japanese laid-open patent open (Kokai) No.47-013221) and patent document 3 (Kokai No.51-029425)) of the catalyst that comprises palladium-phosphoric acid or sulfur-bearing modifier; And the gas-phase one-step oxidation method, wherein use the catalyst (referring to patent document 4 (Kokai No.46-006763)) that comprises the 3rd family's oxygen compound.
And, contain the method for the Preparation of Catalyst acetate of palladium compound and heteropoly acid about use, for example proposed wherein to use the gas-phase one-step oxidation method (referring to patent document 5 (Kokai No.54-57488)) of the catalyst that contains the phosphovanadomolybdic acid palladium.
In addition, the catalyst that openly contains at least a compound that is selected from palladium, heteropoly acid and salt thereof, it can guarantee higher productive rate and selectivity (referring to patent document 6 (Kokai No.7-89896) and patent document 7 (Kokai No.9-67298)) than above-mentioned various catalyst.
These catalyst that contain palladium and heteropoly acid have enough good performance in by ethene and oxygen industrial production acetate.But, the poor heat stability of heteropoly acid; Particularly, promptly unstable under 400 ℃ or higher temperature, therefore require careful stable operation.In addition, be difficult at high temperature carry out sintering, to reclaim catalyst.
On the other hand, existing report composite oxide catalysts is as the catalyst that is generated acetate by ethene and oxygen.These composite oxides are characterised in that the heteropoly acid of comparing, and have higher hear resistance.
EP-A-294,845 (patent documents 8) disclose the method that is generated acetate in the presence of catalyst mixture by ethane, ethene or its mixture and oxygen selective, and this catalyst mixture comprises:
A) calcined catalyst represented of following formula
Mo xV yOr Mo xV yY y
[wherein Y can be one or more metals among Li, Na, Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, Sc, Y, La, Ce, Al, Ti, Zr, Hf, Pb, Nb, Ta, As, Sb, Bi, Cr, W, U, Te, Fe, Co and the Ni, x is 0.5-0.9, y is 0.1-0.4, z is 0.001-1] and
B) ethylene hydration catalyst and/or ethylene oxide catalyst.Suitably, the second catalytic component B is molecular sieve catalyst or palladium-containing catalyst, and the catalyst that singly contains component A or B does not have high-performance.
EP-A-407,091 (patent document 9) disclose the method for producing the mixture that comprises ethene and/or acetate.In this case, the gas that contains ethane and/or ethene and molecular oxygen at high temperature contacts with the carbon monoxide-olefin polymeric that contains composition A, X and Y, and wherein A is Mo dRe eW f(wherein d and f are equal to or greater than 0, and e is greater than 0, and d+e+f=1), X is Cr, Mn, Nb, Ta, Ti, V and/or W, Y is Bi, Ce, Co, Cu, Fe, K, Mg, Ni, P, Pb, Sb, Si, Sn, Tl and/or U.
International open No.99/20592 (patent document 10) brochure discloses in the presence of catalyst shown in the following formula, is generated the method for acetate in the high-temperature region selectivity by ethane, ethene or its mixture and oxygen:
MO aPd bX cY d
[wherein X represents one or more elements among Cr, Mn, Nb, Ta, Ti, V, Te and the W; Y represents one or more elements among B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Au, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl and the U; A=1, b=0.0001-0.01, c=0.4-1 and d=0.005-1].
International open No.00/00284 (patent document 11) brochure discloses MoVNbPd or MoVLaPd as the catalyst that is obtained acetate by ethene and oxygen.
As for the catalyst of tungstenic and noble metal, international open No.98/47850 (patent document 12) brochure discloses the method that is generated acetate by ethane, ethene or its mixture, also discloses the catalyst shown in the following formula:
W aX bY cZ d
[wherein X represents one or more elements among Pd, Pt, Ag and the Au; Y represents one or more elements among V, Nb, Cr, Mn, Fe, Sn, Sb, Cu, Zn, U, Ni and the Bi; Z represents one or more elements among Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Ru, Os, Co, Rh, Ir, B, Al, Ga, In, Tl, Si, Ge, Pb, P, As and the Te; A=1, b＞0, c＞0, d=0-2].But this patent documentation is not mentioned the reactivity when ethene is used as raw material; And, there is not to obtain enough good performance.
In open No.98/47850 (patent document 12) brochure in this world, put down in writing because catalysts containing molybdenum has generated the volatility molybdenum compound unfriendly under reaction condition, and the compound that is generated has reduced activity of such catalysts and selectivity, has therefore proposed mainly to comprise the catalyst system of more stable tungsten.
But, do not set forth the work embodiment of ethene in international open No.98/47850 (patent document 12) brochure as raw material.Therefore it is believed that this catalyst system has high oxidation activity, so that the activation of reactive low ethane, when introducing the ethene of a large amount of high responses, may cause reaction, for example vinyl polymerization or combustion reaction.In any case, the catalyst described in this patent documentation can not be understood that ethene is used as the optimum catalyst system under the raw material condition.
[patent document 1] French Patent (FRP) No.1,448,361
[patent document 2] Kokai No.47-013221
[patent document 3] Kokai No.51-029425
[patent document 4] Kokai No.46-006763
[patent document 5] Kokai No.54-57488
[patent document 6] Kokai No.7-89896
[patent document 7] Kokai No.9-67298
[patent document 8] EP-A-294,845
[patent document 9] EP-A-407,091
[patent document 10] international open No.99/20592 brochure
[patent document 11] international open No.00/00284 brochure
[patent document 12] international open No.98/47850 brochure
Summary of the invention
An object of the present invention is to provide new and effective catalyst, it makes and can generate oxygenatedchemicals (particularly, generating acetate by ethene and oxygen) by alkene and oxygen.
Another object of the present invention provides the above-mentioned Preparation of catalysts method that is used to generate oxygenatedchemicals.
Another object of the present invention provides the method for using this Preparation of Catalyst oxygenatedchemicals.
Through deep investigation, the inventor has found that the catalyst that comprises tungsten, zirconium and palladium unexpectedly can be used as the catalyst (the feasible catalyst that can be obtained acetate by ethene and oxygen high yield, highly selective particularly) that is obtained oxygenatedchemicals by alkene and oxygen.Based on this discovery, the present invention is accomplished.
That is to say that the present invention (I) is the catalyst that is used to prepare oxygenatedchemicals, it is used for by making ethene and the oxygen molecule method at gas phase reaction generation acetate, and this catalyst is by shown in the following formula:
Pd/W aZrO x
[wherein Pd represents to contain palladium compound, and a is the mol ratio of W/Zr, and x is the determined value of oxidation state according to tungsten (W), zirconium (Zr) and palladium (Pd)].
The present invention (II) is preparation the present invention's (I) the method for catalyst that is used to prepare oxygenatedchemicals.
The present invention (III) is the method for Preparation of Catalyst acetate that is used to prepare oxygenatedchemicals of the application of the invention (I).
In addition, the embodiment below for example the present invention includes.
[1] be used to prepare the catalyst of oxygenatedchemicals, it is used for by making the reaction of alkene and oxygen generate the method for oxygenatedchemicals, and described catalyst is by shown in the following formula:
Pd/W aZrO x
[wherein Pd represents to contain palladium compound, and a is the mol ratio of W/Zr, and x is the determined value of oxidation state according to tungsten (W), zirconium (Zr) and palladium (Pd)].
[2] according to the catalyst that is used to prepare oxygenatedchemicals of [1], the content of palladium element is based on 100 parts of W in the wherein said catalyst aZrO xBe 0.001-15 part, the mol ratio of W/Zr is 0.01-5.0.
[3] according to the catalyst that is used to prepare oxygenatedchemicals of [1] or [2], wherein said alkene is ethene, and described oxygenatedchemicals is an acetate.
[4] according to the catalyst that is used to prepare oxygenatedchemicals of [1] or [2], wherein said alkene is propylene, and described oxygenatedchemicals is at least a compound that is selected from acetone, propionic aldehyde, propionic acid and acetate.
[5] catalyst that is used to prepare oxygenatedchemicals of basis [1] or [2], wherein said alkene is be selected from 1-butylene, suitable-2-butylene and anti--2-butylene at least a, and described oxygenatedchemicals is at least a compound that is selected from MEK, hutanal, butyric acid, propionic aldehyde, propionic acid, acetaldehyde and acetate.
[6] a kind of preparation is used to prepare the method for the catalyst of oxygenatedchemicals, and it is preparation according to each the method for catalyst that is used to prepare oxygenatedchemicals of [1]-[5], and described method comprises following first and second steps:
First step:
Make the coexistence of tungsten compound and zirconium compounds, and these compounds are heat-treated, to generate step by compound shown in the following formula:
W aZrO y
[wherein a is the mol ratio of W/Zr, and x is the determined value of oxidation state according to tungsten (W), zirconium (Zr) and palladium (Pd)].
Second step:
Palladium compound is loaded to the W that obtains in the first step aZrO xOn the compound, to obtain being used to preparing the step of the catalyst of oxygenatedchemicals.
[7] be used to prepare the method for the catalyst of oxygenatedchemicals according to the preparation of [6], wherein in described first step, heat treatment temperature is 400-1200 ℃.
[8] a kind of method that is used to prepare oxygenatedchemicals, be included in according to [1]-[5] each be used to prepare under the existence of catalyst of oxygenatedchemicals, alkene and oxygen are reacted in gas phase.
[9] a kind of method that is used to prepare acetate, be included in according to [1]-[5] each be used to prepare under the existence of catalyst of oxygenatedchemicals, ethene and oxygen are reacted in gas phase.
The specific embodiment
Describe the present invention below in detail.Below except as otherwise noted, " part " and " % " expression is quantitatively than based on quality.
(the present invention (I): the catalyst that is used to prepare oxygenatedchemicals)
The present invention (I) is below described.The present invention (I) is the catalyst that is used to prepare oxygenatedchemicals, and it is used for by making alkene, specifically is that ethene and oxygen molecule react the method that generates acetate in gas phase, and this catalyst is by shown in the following formula:
Pd/W aZrO x
[wherein Pd represents to contain palladium compound, and a is the mol ratio of W/Zr, and x is the determined value of oxidation state according to tungsten (W), zirconium (Zr) and palladium (Pd)].
Used alkene is the compound with carbon-carbon double bond among the present invention, for example ethene, propylene, butylene, butadiene, amylene and hexene.Wherein, this alkene is preferably ethene or propylene, more preferably ethene.
Be used to prepare the formation component of the catalyst of oxygenatedchemicals as for the present invention (I), palladium, tungsten, zirconium and oxygen are necessary components.
Be used for preparing the catalyst of oxygenatedchemicals in the present invention (I), can add other element if desired.
(palladium compound)
The palladium compound that is used among the present invention (I) can be any attitude, for example can be compound or element itself, promptly can be ionic state or zero-valent state (so-called metallic state).
Palladium concentration of element in the catalyst is (based on 100 parts of W aZrO x) be preferably 0.001-15 part, 0.005-10 part more preferably, also 0.01-5 part more preferably.If palladium concentration is lower than 0.001 part, then the acetate productive rate may reduce, and if palladium concentration surpasses 15 parts, then because it is expensive noble metal, cost may rise.
(tungsten)
Tungsten in the present invention (I) catalyst is preferably oxidation state, and its valence state is generally 4-6.
(zirconium)
Used zirconium is preferably oxidation state in the present invention (I) catalyst, and its valence state is generally 2-4.
(tungsten-zirconium)
Tungsten-zirconium (W aZrO y) constitute element ratio of component without limits.In the formula, a is the mol ratio of W/Zr, and x is according to the determined value of the oxidation state of tungsten, zirconium and palladium.With regard to mol ratio, tungsten/zirconium (W/Zr) is than being preferably 0.01-5,0.02-3 more preferably, also 0.05-1 more preferably.
(activity of such catalysts)
The high activity of the present invention's (I) catalyst in oxygenatedchemicals (for example acetate) preparation do not set forth with effect is special, and still the content according to the present invention supposes that these are as follows.
The oxide of tungstenic and zirconium generally is the super acid that is known as the wolframic acid zirconium.On the other hand, palladium generally is known as oxidation catalyst.Herein, can know in embodiment of Miao Shuing and the Comparative Examples from behind and see,, almost not make acetate (comparative example 4) even use the catalyst of tungstenic and zirconium.
When use comprises the catalyst of palladium and zirconium, obtain small amount of acetic acid, but space-time yield (being designated hereinafter simply as " STY ") and selection rate low (comparative example 3).Only when palladium and wolframic acid zirconium exist together, just can obtain high acetate STY and selection rate.Think thus to have certain interaction between palladium, tungsten and the zirconium, under this interactional influence, can obtain acetate by ethene and oxygen high activity, highly selective.
(mensuration of ratio of component)
For example, can measure the every kind of element that is comprised in the present invention (I) catalyst suitably: the ratio of component of palladium, tungsten and zirconium by following method.
The catalyst of fixed amount is ground to form uniform powder by mortar etc.This catalyst fines is added in the acid of hydrofluoric acid for example or chloroazotic acid, and under heating stirring and dissolving, to obtain homogeneous solution.With pure water gained solution is diluted to suitable concn, with the solution that obtains being used to analyze.(for example SPS-1700 of Seiko Instruments Inc. production) carries out quantitative analysis to this solution by high-frequency inductor coupled plasma emission spectrometer (hereinafter referred to as " ICP ").For every kind of element,, and can carry out replication by the commercially available standard reagent accuracy of correction analyzer easily.
(the present invention (II): preparation is used to prepare the method for the catalyst of oxygenatedchemicals)
The method that this preparation the present invention (I) is used to prepare the catalyst of oxygenatedchemicals is not particularly limited.That is to say,, can utilize conventional known method, for example flood, precipitation, co-precipitation and kneading as long as above-mentioned catalytic component can be attached in the catalyst.
Consider preparation technology and preparation cost, the preparation method is preferred especially for the following description of the present invention (II).The present invention (II) preparation method is the method that preparation the present invention (I) is used to prepare the catalyst of oxygenatedchemicals.
The present invention (II) comprises following step:
First step:
Make the coexistence of tungsten compound and zirconium compounds, and these compounds are heat-treated, to generate step by compound shown in the following formula:
W aZrO y
[wherein a is the mol ratio of W/Zr, and y is the determined value of oxidation state according to tungsten (W) and zirconium (Zr)];
Second step:
Palladium is loaded to the W that obtains in the first step aZrO xOn the compound, to obtain being used to preparing the step of the catalyst of oxygenatedchemicals.
(the present invention's (II) first step)
The present invention's (II) first step is to make tungsten compound and zirconium compounds coexistence, and these compounds are heat-treated, to generate W aZrO yStep.
(tungsten compound)
The tungsten compound that is used among the present invention (II) can be any tungsten compound.Its object lesson comprises tungstates, tungsten chloride, sulfuric acid tungsten and the alcoxyl tungsten of wolframic acid, for example ammonium metatungstate and ammonium paratungstate.
(zirconium compounds)
The zirconium compounds that is used among the present invention (II) can be any zirconium compounds.Its object lesson comprises zirconium halide, zirconyl oxyhalides zirconium, contains oxygen zirconium nitrate, zirconium hydroxide, zirconia, zirconium acetate and zirconium sulfate.Preferably, this zirconium compounds is a zirconium hydroxide.Zirconium hydroxide can be by making the zirconium compounds hydrolysis with weak base, then drying obtains under the temperature of room temperature-400 ℃.
(appropriate preparation method)
As for obtaining W aZrO yMethod, can wolframic acid be loaded to and be included in the zirconium hydroxide by dipping, spraying etc., but the zirconium hydroxide that preferably will as above obtain be dispersed in the water-soluble ammonium tungstate aqueous solution, at 300 ℃ or more dehydrate under the low temperature, follow sintering under predetermined temperature, to obtain W aZrO y
(oxide of zirconium and tungsten)
When sintering contained the oxide of zirconium and tungsten, catalytic activity can be strengthened.Sintering temperature is preferably 400-1200 ℃, more preferably 500-1000 ℃.If this sintering temperature is lower than 400 ℃, then can not between zirconia and wolframic acid, form keyed jointing satisfactorily, and activity may reduce, if and this temperature is above 1200 ℃, then surface area seriously reduces, thereby can not guarantee and response matrix between abundant contact area, so the gained activity of such catalysts may reduce.
The oxide that gained contains tungsten and zirconium is used as the carrier of palladium compound in the present invention's (II) second step, and the shape of above carrier is not particularly limited.Its object lesson includes but not limited to Powdered, spherical and graininess.Also this oxide can be clayed into power fully, and can further be shaped to sheet, column etc.The particle diameter of used above carrier is not particularly limited among the present invention.Use this to be used under the situation of alkene and oxygen catalyst for reaction in fixed-bed tube reactor, when carrier when being spherical, its particle diameter is preferably 1-10mm, more preferably 2-8mm.Under the situation of in tubular reactor, reacting by catalyst filling, if particle diameter is less than 1mm, then in the gas flow process, produce big pressure drop, gas circulation may not can be carried out effectively, if and particle diameter surpasses 10mm, then reacting gas can not be diffused into catalyst inside, and catalytic reaction may not carried out effectively.
Thus, can in first step, obtain W aZrO y
(the present invention's (II) second step)
The present invention's (II) second step is that palladium compound is loaded to the W that obtains in the first step aZrO yOn, to obtain being used to prepare the catalyst (Pd/W of oxygenatedchemicals aZrO x) step.
At this, usually, X=Y, but x can be different with y.
(palladium starting compound)
Palladium starting compound used in the present invention's (II) second step is not particularly limited.Its object lesson comprises chloride, for example palladium bichloride; Acylate, for example acid chloride; And nitrate, for example palladium nitrate.Other example includes organic compounds, and for example acetylacetonate, nitrile and ammonium are as the Pd complex compound of part.
(load of palladium compound)
Palladium compound is loaded to the W that obtains in the first step aZrO yOn method can be any method.Its object lesson comprises starting compound is dissolved in suitable solvent (for example water, acetone) or organic or inorganic acid (for example hydrochloric acid, nitric acid, acetate) or its solution, and this compound is directly or indirectly loaded to method on the superficial layer.As for direct load, for example can use infusion process or spray-on process.
(reduction of carried catalyst is handled)
Palladium compound is under the situation of palladium salt in the present invention (II) second step, can be with resulting carried catalyst reduction, and palladium salt can be converted into Metal Palladium thus.This reduction is handled and is preferably undertaken by reducing agent, is preferably the gaseous reducing agent under the normal reducing condition.
This reducing agent is not particularly limited, but its example comprises hydrogen, ethene, methyl alcohol and CO, hydrazine.Wherein, preferred hydrogen and ethene, more preferably hydrogen.
Reducing under the situation about handling, treatment temperature is not particularly limited, but preferred under 50-600 ℃, more preferably 100-500 ℃ of catalyst of in the present invention's second step, obtaining of heating down.
Processing pressure is not particularly limited, but considers equipment, and the pressure of 0.0MPa in the reality (gauge pressure)-3.0MPa (gauge pressure) is favourable.Processing pressure is 0.1MPa (gauge pressure)-1.5MPa (gauge pressure) more preferably.
Under the situation of carrying gaseous reducing agent, can use the reducing agent of any concentration.If wish, can use nitrogen, carbon dioxide, rare gas etc. as diluent.And, in the presence of vaporize water, can allow existence such as ethene, hydrogen and reduce.In addition, can be loaded into by the catalyst that makes in second step with the present invention (II) in the reactor of reaction system, after it being reduced, introduce oxygen again, thereby generate acetate by ethene and oxygen with ethene.
The mist that contains the gaseous state reducing agent is preferably being 10-15000hr under the standard conditions -1, more preferably 100-8000hr -1Air speed (hereinafter referred to as " SV ") pass through catalyst.
Processing mode is not particularly limited, but the wherein above-mentioned catalyst of preferred use is seated in the fixed bed in the corrosion-resistant reaction tube, and this is favourable in practice.
Thus, can obtain to be used to prepare the catalyst (I) of oxygenatedchemicals.(method that is used to prepare the Preparation of Catalyst oxygenatedchemicals of oxygenatedchemicals by use)
The present invention (III) is below described.The present invention (III) is the catalyst of the application of the invention (I) is prepared oxygenatedchemicals (for example acetate) by alkene (specifically being ethene) and oxygen a method.
(alkene)
Used alkene is the compound with the two keys of C-C, for example ethene, propylene, butylene, butadiene, amylene and hexene among the present invention.Wherein, this alkene is ethene or propylene preferably, more preferably ethene.
Prepare in the method for oxygenatedchemicals in the present invention (III), the reaction temperature when making alkene (for example ethene) and oxygen reaction generate oxygenatedchemicals (for example acetate) is not particularly limited.This reaction temperature is preferably 100-300 ℃, more preferably 120-250 ℃.Reaction pressure is not particularly limited, but considers equipment, and the pressure of 0.0MPa in the reality (gauge pressure)-3.0MPa (gauge pressure) is favourable.Reaction pressure is 0.1MPa (gauge pressure)-1.5MPa (gauge pressure) more preferably.
Prepare in the method for oxygen-containing gas in the present invention (III), the gas of supply response system comprises raw material olefin (for example ethene) and oxygen; If wish, can also use nitrogen, carbon dioxide, rare gas etc. as diluent.
Based on the gas gross of supply response system, raw material olefin, for example the amount of ethene accounts for 5-80 volume %, preferred 8-60 volume %, oxygen accounts for 1-15 volume %, preferred 3-12 volume %.
In this reaction system, when having water in the reaction system, obviously strengthened catalyst in preparation oxygenatedchemicals, for example activity in the acetate and selectivity, and active lifetime.In reacting gas, the content of water vapour is suitably 1-50 volume %, is preferably 5-40 volume %.
At the present invention (III) preparation oxygenatedchemicals, for example in the method for acetate, raw material olefin (for example ethene) is preferably high-purity alkene, but other gas (for example rudimentary saturated hydrocarbons, for example methane, ethane and propane) can be mixed in this alkene.Oxygen can be with by inert gas, and for example oxygen form supply of nitrogen or carbonic acid gas dilution is for example with the form of air; But under the situation of this reacting gas of circulation, generally advantageously use high-concentration oxygen, its concentration is preferably 99% or higher.
(reaction condition)
The reaction mixture gas body is preferably being 10-15 under the standard conditions, 000hr -1, more preferably 300-8,000hr -1SV pass through catalyst.
Reactive mode is not particularly limited, and can use the known method of fixed bed for example or fluid bed.The fixed bed that uses wherein above-mentioned catalyst to be seated in the corrosion-resistant reaction tube is preferred, and favourable in practice.
Embodiment
Followingly describe the present invention in more detail, but the invention is not restricted to this with reference to embodiment and comparative example.
[use of water]
In all embodiments, used water is deionized water.
[embodiment 1]
With zirconium hydroxide [Zr (OH) 4, Daiichi KigensoKagaku Kogyo Co., Ltd. produce] and be immersed in ammonium metatungstate [(NH 4) 10W 12O 41.5H 2O, Wako Pure Chemical Industries, Ltd. produce] in the aqueous solution, to obtain 0.1 W/Zr mol ratio; By evaporate do solid, under 100 ℃ in air further dry one day one evening, then under 800 ℃ in air sintering 3 hours, to obtain tungsten-zirconium (W aZrO y).
Subsequently, weighing palladium bichloride [PdCl 2.H 2O, Wako Pure Chemical Industries, Ltd. produce] the HCl aqueous solution, with the W that obtains obtaining based on more than 100 parts aZrO y, the palladium element is 1 part.Subsequently, with W aZrO yBe immersed in this solution, by evaporate do solid, then under 400 ℃ in air sintering 5 hours, obtain being used to prepare the catalyst 1 of acetate.
[embodiment 2-5]
These embodiment are undertaken by the mode identical with embodiment 1, and difference is that the value shown in the W/Zr mol ratio according to the form below 1 changes.
Table 1:
Embodiment Be used to prepare the catalyst of acetate The W/Zr mol ratio 100 parts of W aZrO yThe mass parts of middle Pd
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 1 2 3 4 5 0.1 0.2 0.3 0.4 0.5 1.0 1.0 1.0 1.0 1.0
[embodiment 6-10]
These embodiment are undertaken by the mode identical with embodiment 1, and difference is Pd and W aZrO yQuality change than the value shown in the according to the form below 2.
Table 2:
Embodiment Be used to prepare the catalyst of acetate 100 parts of W aZrO yThe mass parts of middle Pd
Embodiment 6 embodiment 7 embodiment 8 6 7 8 0.5 1.5 2.0
[comparative example 1]
The HCl aqueous solution of palladium bichloride is immersed in 100 parts of zirconium hydroxides, obtaining 1.0 parts ratio, by evaporate do solid, then under 400 ℃ air drying 5 hours, obtain being used to prepare the catalyst 9 of acetate.
[comparative example 2]
Zirconium hydroxide is immersed in the ammonium metatungstate aqueous solution, to obtain 0.1 W/Zr mol ratio; By evaporate do solid, under 100 ℃ in air further dry one day one evening, then under 800 ℃ in air sintering 3 hours, to obtain being used to prepare the catalyst 10 of acetate.
[comparative example 3]
According to the embodiment 1 of Kokai No.7-89896, preparation contains the catalyst of palladium and heteropoly acid.
Silica carrier (250ml) is immersed in contains 10g tetrachloro-palladium acid sodium [Na 2PdCl 4, TanakaKikinzoku Kogyo K.K. produces] the aqueous solution in, this carrier absorption all after the amount, is added to 200ml again and contains in the aqueous solution of 18g sodium metasilicate, then leaves standstill 20 hours.Subsequently, to the 85% hydrazine aqueous solution that wherein adds 10ml, so that the tetrachloro-palladium acid sodium reduction is become Metal Palladium.Wash the carrier of gained containing metal palladium with water, 110 ℃ dry 4 hours down, add to again in the aqueous solution that 90ml contains 20 parts of (based on 100 parts of carriers) silico-tungstic acids; After carrier absorption is all measured, descended dry 4 hours at 110 ℃ again, to obtain being used to prepare the catalyst 11 of acetate.
[embodiment 9-16 and comparative example 4-6]
The catalyst 1-3 that is prepared acetate being used for of preparing that the catalyst 1-9 of acetate and comparative example 1-3 obtain being used for of obtaining among every 2ml embodiment 1-9 is loaded into the reaction tube (internal diameter: 10mm) that SUS316 makes.For palladium bichloride reduction preliminary treatment, under 300 ℃, carry hydrogen: the gaseous mixture of helium=1: 11 hour with 60ml/min.
Subsequently, making that the reaction temperature of catalyst layer is 150 ℃, reaction pressure is under the condition of 0.4MPaG (gauge pressure), will be with volume ratio 50: 7: 30: 13 ethene: oxygen: steam: nitrogen mixes the gas that obtains with 3000hr -1Air speed introduce, carry out obtaining the reaction of acetate thus by ethene and oxygen.
As for the analytical method in the reaction, will be by whole exit gas coolings of catalyst packed layer; For the reaction liquid that condensation is collected, reclaim all amounts, and by gas chromatographic analysis.For the uncondensed gas that does not have condensation, measure the whole uncondensed gas that flow out in sample time, and therefrom take out part, by its composition of gas chromatographic analysis.
Use each catalyst, carry out ethylene oxidation reactions.The results are shown in the table 3.
Result according to following every kind of product of formula assessment.
(1) conversion ratio (%)=((infeeding the molal quantity of raw material)-(molal quantity of unreacting material))/(infeeding the molal quantity of raw material) * 100
(2) selection rate (%)=((molal quantity of every kind of product) * (carbon number of every kind of product)/(infeeding the carbon number of ethene))/(molal quantity of reacting ethylene) * 100
(3) STY of acetate (g/hL)=(acetate is molal quantity per hour)/(catalyst volume (L))
The technology practicality
Aforesaid, the catalyst of the application of the invention (I) can and generate oxygenatedchemicals in high selectivity by alkene and oxygen high yield.
[table 3]
Table 3: the result of ethylene oxidation reactions
Be used to prepare the catalyst of acetate Conversion ratio % Selection rate % Acetate STY, g/hL
Ethene Oxygen Acetate Acetaldehyde Ethanol CO2 CO
Embodiment 9 embodiment 10 embodiment 1l embodiment 12 embodiment 13 embodiment 14 embodiment 15 embodiment 16 comparative examples 4 comparative examples 5 comparative examples 6 1 2 3 4 5 6 7 8 9 10 11 1.1 1.7 1.7 1.5 1.2 0.5 1.4 1.7 0.1 0.1 1.1 20.6 24.8 22.7 22.4 17.1 9.3 21.7 24.8 4.2 0.2 18.7 76.2 79.7 79.7 71.8 74.1 75.1 77.3 79.7 57.9 0 52.8 1.6 0.8 0.8 0.6 0.9 1.5 0.8 0.8 3.5 23 0.9 0 0 0 0 0 0 0 0 0 73 0.4 21.5 19.0 19.1 27.0 24.6 23.4 21.3 19.0 38.6 2.3 45.9 0.7 0.5 0.4 0.6 0.3 0.0 0.6 0.5 0.0 0.0 0.0 32.2 51.9 51.1 41.2 34.5 54.0 48.0 51.9 2.4 0.0 22.1

Claims (9)

1. catalyst that is used to prepare oxygenatedchemicals, it is used for by making the reaction of alkene and oxygen generate the method for oxygenatedchemicals, and described catalyst is by shown in the following formula:
Pd/W aZrO x
[wherein Pd contains palladium compound, and a is the mol ratio of W/Zr, and x is the determined value of oxidation state according to tungsten (W), zirconium (Zr) and palladium (Pd)].
2. according to the catalyst that is used to prepare oxygenatedchemicals of claim 1, the content of palladium element is 0.001-15 part in the wherein said catalyst, and the mol ratio of W/Zr is 0.01-5.0.
3. according to the catalyst that is used to prepare oxygenatedchemicals of claim 1, wherein said alkene is ethene, and described oxygenatedchemicals is an acetate.
4. according to the catalyst that is used to prepare oxygenatedchemicals of claim 1, wherein said alkene is propylene, and described oxygenatedchemicals is at least a compound that is selected from acetone, propionic aldehyde, propionic acid and the acetate.
5. according to the catalyst that is used to prepare oxygenatedchemicals of claim 1, wherein said alkene is to be selected from least a in 1-butylene, suitable-2-butylene and anti--2-butylene, and described oxygenatedchemicals is at least a compound that is selected from MEK, hutanal, butyric acid, propionic aldehyde, propionic acid, acetaldehyde and the acetate.
6. method for preparing the catalyst that is used to prepare oxygenatedchemicals, it is preparation according to each the method for catalyst that is used to prepare oxygenatedchemicals of claim 1-5, described method comprises following first and second steps:
First step:
Make the coexistence of tungsten compound and zirconium compounds, and these compounds are heat-treated, to generate step by compound shown in the following formula:
W aZrO y
[wherein a is the mol ratio of W/Zr, and x is the determined value of oxidation state according to tungsten (W) and zirconium (Zr)];
Second step:
Palladium compound is loaded to the W that obtains in the first step aZrO xOn the compound, to obtain being used to preparing the step of the catalyst of oxygenatedchemicals.
7. be used to prepare the method for the catalyst of oxygenatedchemicals according to the preparation of claim 6, wherein in described first step, heat treatment temperature is 400-1200 ℃.
8. method that is used to prepare oxygenatedchemicals, be included in according to claim 1 be used to prepare under the existence of catalyst of oxygenatedchemicals, alkene and oxygen are reacted in gas phase.
9. method that is used to prepare acetate, be included in according to claim 1 be used to prepare under the existence of catalyst of oxygenatedchemicals, ethene and oxygen are reacted in gas phase.
CN2005800106062A 2004-03-29 2005-03-28 Palladium, tungsten and zirconium-based catalyst for production of oxygen-containing compound, production process of the catalyst, and production process of oxygen-containing compound using the cataly Expired - Fee Related CN1938085B (en)

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Publication number Priority date Publication date Assignee Title
FR1448361A (en) 1964-08-21 1966-08-05 Ici Ltd Acetic acid manufacturing process
GB1094197A (en) * 1964-08-21 1967-12-06 Ici Ltd Production of acetic acid
JPS4713221U (en) 1971-03-10 1972-10-17
US3970697A (en) * 1974-07-01 1976-07-20 National Distillers And Chemical Corporation Oxidation of ethylene to acetic acid
JPS5457488A (en) 1977-10-17 1979-05-09 Sagami Chem Res Center Acetic acid production catalyst
GB8915410D0 (en) 1989-07-05 1989-08-23 Bp Chem Int Ltd Chemical process
US5162578A (en) 1987-06-12 1992-11-10 Union Carbide Chemicals & Plastics Technology Corporation Acetic acid from ethane, ethylene and oxygen
JP3343982B2 (en) 1993-04-06 2002-11-11 昭和電工株式会社 Acetic acid production method
TW295579B (en) * 1993-04-06 1997-01-11 Showa Denko Kk
DE69420849T2 (en) 1993-07-22 2000-04-20 Mobil Oil Corp METHOD FOR PRODUCING A MODIFIED SOLID OXIDE CATALYST
US5902767A (en) * 1993-08-03 1999-05-11 Mobil Oil Corporation Catalyst having an acidic solid oxide component and a group IB metal or metal oxide component
JP3232971B2 (en) 1995-08-29 2001-11-26 昭和電工株式会社 Catalyst for producing acetic acid, method for producing the catalyst, and method for producing acetic acid using the catalyst
DE19630832A1 (en) * 1996-07-31 1998-02-05 Hoechst Ag Process for the selective production of acetic acid
DE19717076A1 (en) 1997-04-23 1998-10-29 Hoechst Ag Catalyst and process for the catalytic oxidation of ethane to acetic acid
DE19745902A1 (en) * 1997-10-17 1999-04-22 Hoechst Ag Selective production of acetic acid with high space-time yield
US6127432A (en) * 1998-01-29 2000-10-03 Union Carbide Chemicals & Plastics Technology Corporation Processes for preparing oxygenates and catalysts therefor
EP1063010B1 (en) 1998-03-09 2008-07-02 Osaka Gas Company Limited Method for removing methane from exhaust gas
US6028221A (en) 1998-06-29 2000-02-22 Saudi Basic Industries Corporation Catalyst systems for the one step gas phase production of acetic acid from ethylene and methods of making and using the same
GB9819221D0 (en) * 1998-09-04 1998-10-28 Bp Chem Int Ltd Process for the production of acetic acid
JP2001232207A (en) * 2000-02-24 2001-08-28 Idemitsu Petrochem Co Ltd Oxidative dehydrogenation catalyst of alkanes and method for producing olefins or oxygen-containing compound using the same
FR2841797B1 (en) * 2002-07-03 2005-08-05 Centre Nat Rech Scient CATALYSTS BASED ON TUNGSTEN

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